JPS5833316B2 - Manufacturing method of amorphous alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an amorphous alloy.

In recent years, amorphous alloys have begun to attract attention for their structure, physical properties (particularly thermal, electrical, and magnetic properties), and even mechanical properties.

That is, the following can be considered as general features of amorphous alloys.

(1) The mechanical strength is higher than that of practical metal materials and is intermediate between that of practical metal materials and whiskers.

(2) The rigidity is 20 to 40% lower than that of crystalline metals.

(3) Almost no work hardening.

(4) Electrical resistance is generally high.

(5) Corrosion resistance and properties are significantly improved by adding Cr, etc.

(6) It is possible to manufacture products with high magnetic permeability.

Conventionally, known methods for manufacturing this type of amorphous alloy include sputtering, melt quenching (e.g. gun method, piston anvil method, rolling method, centrifugal method), etc., but the latter quenching method is more commonly practiced.

According to this method, an Fe-based metal and two or more types of amorphous elements (for example, P, C, B, and Si) are once dissolved, cooled, crushed, and melted again. It is made to become amorphous by rapidly cooling it by spraying or the like.

As a result, although it is possible to form an amorphous alloy film,
Since Fe has a high melting point, it is necessary to contain at least two types of amorphous elements in order to lower the eutectic temperature and facilitate manufacturing.

Therefore, it is impossible to produce an alloy consisting of two elements, for example Fe--P, and the rapid cooling process is extremely troublesome.

Furthermore, it is difficult to control the thickness of the alloy coating or to vary the shape of the alloy coating.

The present invention is intended to correct the above-mentioned deficiencies. 8-30ft calculated as divalent Fe ion, NaH2PO2・H2O, which increases to /l
Pi
-1i, o~2.2, temperature 30~50℃, current density 5~
This relates to a method for producing an amorphous alloy in which an amorphous alloy containing mainly Fe and P is obtained by electroplating under conditions of 20 A/d m2,
The second invention is calculated as FeSO4・7H20 and is 1
Divalent Fe ions equivalent to 00 to 500 g/l, Ni ions and/or Co less than 109/l calculated as nickel sulfamate or cobalt sulfamate
8 to 3 calculated as ion, NaH2PO□・H2O
Using a plating bath mainly containing hypophosphorous acid and/or hypophosphite corresponding to 0 ft/l and divalent Cu ions of 4 X 10-' to 8 X 10-' moA%, pH 1, 0-2.2, temperature 30-50℃, current density 5
An amorphous alloy containing mainly 60 to 88 atomic % Fe, 10 atomic % or less Ni and/or Co, and 12 to 30 atomic % P by electroplating under the condition of ~20 people/dm2 The present invention relates to a method for producing an amorphous alloy that obtains the following.

By these methods, it is possible to extremely easily produce an amorphous alloy having the above-mentioned features using one type of amorphous element, and the amount of the amorphous element can be reduced.
The thickness and shape of the alloy can be controlled very easily, and a glossy amorphous alloy can be obtained.

In the method according to the first invention, divalent Fe ions, which are the main components of the above-mentioned plating bath, include ferrous sulfate FeSO4,
It can be obtained from sources that supply Fe2+, such as iron sulfamate, Fe(NH2SO3)2, or mixtures thereof.

The other main component of the plating bath is a source of P, and hypophosphorous acid Hs PO2, hypophosphite, or a mixture thereof is used. Sodium NaH2PO2, potassium hypophosphite KH
Examples include 2Po 2 and the like.

Furthermore, in the method according to the second invention, among the main components of the above-mentioned plating bath, divalent Fe ions are ferrous sulfate Fe
It is obtained from sources that supply Fe2+, such as iron sulfamate, Fe(NH2SO3)2, or a mixture thereof, and nickel sulfamate, nickel sulfate, etc. are used as the source of Ni ions, and the source of Co ions. Cobalt sulfamate, cobalt sulfate, etc. are used as sources of P, and hypophosphorous acid H3 is used as a source of P.
PO2, hypophosphite, or a mixture thereof may be used.

This hypophosphite is sodium hypophosphite, NaH.
2PO2, potassium hypophosphite KH2PO2, and the like.

Next, to roughly describe the principle of plating, for example, FeSO
4 dissociates into Fe2+ and SO42-, and Fe2+ moves to the cathode side, where it is reduced and electrodeposited as Fe.

Also, hypophosphite, such as NaH2PO2, is once converted to Na+
and (H2PO2)-, and these become NaOH and H3PO2 by H2O, but among these, NaOH changes to Na2804 because the pH of the plating bath is low.

Therefore, hypophosphite eventually becomes H3PO2, and it is thought that P is supplied from this.

Note that Na in NaPH20□ acts to stabilize this reagent.

However, the amorphous alloy obtained in this state is mostly satin-plated and has a surface roughness of 20 to 50μ.
It is relatively rough.

To this end, in the present invention, the above-mentioned plating bath contains Cu2+, which acts as a brightener, to incorporate Cu into the amorphous alloy.

As a result, an amorphous alloy mainly composed of Fe and P
By containing , a glossy surface can be obtained, and a mirror-like glossy plating can be obtained.

In this case, the divalent copper ions Cu2+ to be added include copper sulfate Cu5O+・5H20, copper sulfamate Cu (NH2
S Os )2, cupric chloride CuC132, etc., or a mixture thereof.

Note that these Cu2+ supply substances are easily soluble in the plating bath.

The plating bath according to the first invention may consist of the following basic composition and is preferably electroplated under the following conditions.

Fe 804 ・7H20 L-ascorbic acid NaH2PO2'H2O CuSO4・5H20 pH 100-500 t/13 2-10 t/lI 8-30 t/1t O001-2g/1 1.0-2.2 Current density 5- 20 A7'dm2 Bath Temperature: 30-50°C The plating bath according to the second invention may have the following basic composition, and is preferably electroplated under the following conditions.

Fe5017H20100-50011/II Nickel and/or Sulfamic acid 10 t/13 or less Cobalt famic acid L-Ascorbic acid 2-10 Y/IN
aH2PO2・I2,0 8~30
f/1CuSO+・5H200,01~2? /13p
I (1,0-2.2 Current density 5-20 A7'dm2 Bath temperature 30-50°C In these cases L-ascorbic acid acts as a stabilizer for Fe2+.

In addition to the components of the above basic composition, as a source of Ni, an appropriate amount of nickel sulfate NiSO4,7)I20. As a source of Co, an appropriate amount of cobalt sulfate Co50. ．． 7H20 may be added.

Further, boric acid HsBOa and ammonium chloride NH4Cl may be added, but these generally act as brighteners in Ni plating, and C4 of NH4Cl facilitates dissolving Fe50+.

Note that the amount of Cu 804 ・5H20 added is 0.01 to 2.
The reason for setting f/13 (4X10-5 to 8X10-3 mol/l) is that if the amount is less than 0.01//, the plating will be too shiny, and if it exceeds 2fI/l, the plating will become glossy. This is because if the amount is too large, Cu will precipitate on the plating surface, making it difficult to produce gloss.

Additionally, if the pH falls outside the above range and becomes less than 1.0, the concentration of P will increase and the adhesion of the plating will become poor; if the pH exceeds 2.2, the plating will adhere but it will be difficult to form an amorphous plating. Become.

Furthermore, if the current density is outside the above range and is less than 5 A/dm2, plating becomes difficult, and if it exceeds 20 A/dm2, the electrodes will be burnt, which is not preferable.

Furthermore, if the bath temperature is too high, the components of the plating bath will precipitate.

Furthermore, when we investigated the relationship between the plating bath temperature and the oxidation-reduction potential of the Fe system, we found that the oxidation-reduction potential between Fe and Fe2+ is -
It is 0.47 mV and is constant at pH=o~6.

In addition, we investigated the relationship between the pH of the plating bath and the P-based redox potential, and found that in order to plate a Fe-P-based eutectic alloy made of Fe and P eutectic, the above redox potential (- 0.47 mV) and the redox potential with respect to P must be close.

However, if the pH becomes 2 or more, P and H3PO2 or H
It was found that the oxidation-reduction potential between Fe and 2PO2 tends to be very low, and therefore, at the above-mentioned oxidation-reduction potential of Fe, P is plated and it is difficult to obtain an amorphous material.

Therefore, in order to obtain an amorphous alloy with the redox potential of P close to the redox potential of Fe, it is necessary to adjust the pH to 2.2 or less, preferably 1.5 to 2.0. .

Furthermore, the plating bath according to the present invention may have a modified basic composition, and instead of FeSO4.7H20) ~ I
mol of iron sulfamate may be used, and for this modified basic composition O to O for low activity and gloss imparting.
Urea of 130 fI/A', ammonium sulfamate of 20 to 609/1, which adjusts the pH and acts as a buffer, and a small amount of brightener may be added, respectively.

In addition, by adding an appropriate amount of nickel sulfamate or cobalt sulfamate, Fe-Ni or Co-P
It can also be an amorphous alloy.

The amorphous alloy produced by the method according to the first invention has Fe and P as main components, and the amorphous alloy produced by the method according to the second invention contains Fe, Ni and/or Co. and P as main components, and Fe is 60 to 88a
t%, Ni and/or C.

is preferably 10 at % or less, P is preferably 12 to 30 at %, and it is also desirable that Cu be contained in a small amount corresponding to the amount of the above-mentioned Cu2+ supplying substance added.

The reason for setting Fe to 60 to 88 at% (ratio of the number of atoms) is that if Fe is less than 60 at%, plating will not adhere well and the P concentration will increase, reducing the magnetic flux density Bs. This is because if it exceeds 88 at%, the P concentration decreases and it becomes difficult to form an amorphous alloy.

In addition, the P content is set at 12 to 30 at% because it is in the opposite relationship to the above-mentioned Fe ratio, so if P is less than 12 at%, it is difficult to obtain an amorphous alloy, and if P exceeds 30 at%, the electrical resistance is high. This is because if it becomes too much, the adhesion of plating becomes poor and the magnetic flux density Bs decreases.

Note that each of the amorphous alloys according to the first invention and the second invention can further contain 1 to 2 at% of Cr, etc. to improve the corrosion resistance of the alloy, but in this case, Cr is
If Fe2+ is not present in the plating bath as 3+, F
This is undesirable because it oxidizes to e3+.

As explained above, according to the present invention, a supply source of Fe, for example, Fe50+, and a supply source of P, for example, NaH
Since electroplating is performed using an acidic plating bath containing 2PO2 as the main component, Fe
It has become possible to manufacture an amorphous alloy consisting of two elements -P.

Since the plating method is used, the operation is extremely simple compared to conventional methods, and the amount of P, which is an amorphous element, is relatively small.

Furthermore, since it is performed by plating, the thickness and shape of the alloy film can be controlled very easily.

Importantly, however, the addition of Cu2+ makes it possible to obtain a shiny plating alloy.

The amorphous alloy according to the present invention has the characteristics of conventional amorphous alloys.

In other words, it has high mechanical strength, almost no work hardening, relatively low rigidity, high electrical resistance, and high magnetic permeability, making it suitable for small items that require strength, including magnetic materials. Very useful for parts, composite materials, plates, wires, etc.

As an example of manufacturing an amorphous alloy using the above-described plating bath according to the present invention, as a pretreatment for plating, an object to be plated, such as a Cu test piece, is first degreased and cleaned with trichlene vapor, and then, for example, After cathode cleaning with 30fI/A' Metalex W Special (trade name, manufactured by MacDermid), the plate was washed with water, and the main plating was started.

In addition, as another pretreatment, the Al specimen was cleaned with trichlene vapor, then Cu struck (i.e., applying a thin Cu film) from copper cyanide by Zn or Sn substitution method, and then Cu plated from copper pyrophosphate. I later went into book plating.

This plating was carried out using plating baths according to the following examples of the present invention.

Example 1 An acidic plating bath having the following composition was prepared.

Iron sulfamate (as iron) 56fl/IL-
Ascorbic acid 5 Y/1jH3B03
20 ft/1 ammonium sulfamate 60 f? /l;NaH2PO
2.H2O21,2ft/13 saccharin sodium
2ft/ICu 804 ・5H200,
2ft/13 and plating was carried out using this plating bath under the following conditions.

pH 1,72 Current density 71'Jdm2 Bath temperature 40°C A shiny Fe-P alloy was obtained from the above plating bath.

When X-ray diffraction was performed on this alloy, a broad spectrum was obtained, but α
- Comparison with the spectrum of iron showed that the alloy according to this example was amorphous.

As a result of analysis, the alloy according to this example has Fe79.
It had a composition of 2P20.5 Cuo, 33.

As a result of measuring the magnetic quantity of this alloy using a magnetic balance, the magnetic flux density Bs was 14,100 gauss.

Also, the initial magnetic permeability μ' I when a magnetic field of IKHz is applied
KHz was 1700.

In this example, the brightener Cu2+ was replaced with Cu5O
Although it was added as r5H20, Cu was incorporated into the amorphous alloy as a result of electroplating, and as shown in the drawing, there is a linear relationship between the added CuSO4.5H20 and the incorporated Cu. I found out.

In this case, the amount added is 0.01 to 2' as mentioned above. /
It was found that a small amount of it (0.2'?/13 in this example) does not cause much change in BS, etc.

The thickness of the obtained plating film could be freely changed by controlling the concentration of the components of the plating bath, the pH 1 current density, etc.

In addition, C formed on the surface of the object to be plated by the above-mentioned pretreatment.
If a photoresist layer with a predetermined pattern is applied to the surface of the U-film, a plating film can be applied to areas where this photoresist layer does not exist, so it is easy to apply a plating film with various patterns depending on the shape of the photoresist layer. was able to form.

Example 2 In this example, an acidic plating bath having the following composition was prepared.

Fe50+ ・7H20300ft/A? L-ascorbic acid 5g/1H3BO330?
/II NaH2PO2・H208,5S'/IINH4C12
0ft/A' CuSO4.5H201, Oft/l Using this plating bath, plating was performed under the following conditions.

pH 1.8 Current density 10A/dm2 Bath 40°C In the above plating bath, FeS04 is used as the Fe supply source, NaH2PO2・N20 is lower than in Example 1, while CuSO4 is increased. A shiny Fe--P based amorphous alloy, Fe7B, 5P19.9 CuLa, was produced in the same manner as described in Example 1 above.

I was able to do it.

Further, this magnetic flux density Bs was 14,000 gauss.

Example 3 In this example, 2.0% of nickel sulfamate was added to the plating bath described in Example 1 above. When plating was performed with the addition of /l, a shiny Fe-N1-P-based amorphous alloy was obtained.

Example 4 In this example, 10f/7 of nickel sulfamate was added to the plating bath described in Example 1 and plating was performed, but the resulting alloy plating film was the same as that obtained in Example 3. The content of Ni was higher than that of the original.

Example 5 In this example, when plating was performed by adding 51/l of cobalt sulfamate to the plating bath described in Example 1, shiny Fe-C was obtained.

-P-based amorphous alloy was obtained.

[Brief explanation of drawings]

The drawing shows one embodiment of the present invention, and is a graph showing the relationship between the amount of Cu5O+.5N20 added to the plating bath and the amount of Cu contained in the amorphous alloy.

Claims (1)

[Claims] 100 to 5 calculated as I Fe50+・7H20
00? /l divalent Fe ion, NaH2PO2
・Hypophosphorous acid and/or hypophosphite corresponding to 8 to 30 f/11 calculated as H2O and 4X10-5 to
Using a plating bath mainly containing divalent Cu ions of 8X 10-"mo, pH 1.0 to 2.2, temperature 3.
A method for producing an amorphous alloy, in which an amorphous alloy containing mainly Fe and P is obtained by electroplating under conditions of -0 to 50°C and a current density of 5 to 20A7/dm2. 2 Calculated as Fe50+7H20 100~50
Divalent Fe ions equivalent to 01i/l, Ni ions and/or Co ions of 10fI/l or less calculated as nickel sulfamate or cobalt sulfamate, 8 to 30f/l calculated as NaH2PO2・H2O
Hypophosphorous acid and/or hypophosphite corresponding to / and 4
Using a plating bath mainly containing divalent Cu ions of X 10-' to 8 X 10-3 mo4/l, p
H1.0~2.2, temperature 30~50℃, current density 5~2
By electroplating under conditions of 0 A/dm2, an amorphous alloy containing mainly 60 to 88 at% Fe, up to 10 at% Ni and/or Co, and 12 to 30 at% P is prepared. A method for producing an amorphous alloy.